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United States Patent 2,824,094 CHRoMIUMeo TAINm AzonYEsr FFs .Nopraw nApplication sept e 1955 M .1 seria1No.5,3 ,Q55

Claims priority, application Switzerland. October 8, 1954 7 Claims. 21.260E146) The present'invention is concerned withnew azo dyestutfs whichcontain heavy metal, the production and use thereof for the fast dyeingof polypeptidefibres such as wool, superpolyamidesandsuperpolyurethanes. ln particular, it is concerned with theinfluencing of the dyeing properties of metal containing unsulphonatedazo dyestuifs by incorporating complex formers in the metal containingdyestuff molecule, which formers are different from the metallisable azodyestuff. Finally, it isalso concerned withthe production ofunsymmetrical, but comparatively stable, heavy metal complexes by theco-ordination of a metallisable azo dyestufiwhich can occupy more than 3co-ordination positions at the metal atom; and "a complex former whichcan occupy less than 3 co-ordination positions at the metal atom, with aco-ordinative hexavalent heavy metal atom.

It is known-that, in comparison with the metal free azo dyestuff, thealtered dyeing behaviour on dyeing wool of the complex chromium compoundwhich contains one metal atom bound to each dyestulr" molecule is due tothe fixation ofthe chromium atom on the substratum. (See WJEHdEI and A.Mi iller, Melliands Textilberic hte 19, 181 (1938).) In metalliseddyestuffs of these "types there has not been a lack of attempts,therefore, tohinder the disadvantageous results of a too early fixing ofthe metal on the wool by masking the chromium bound in complex linkagein the complete dyestufl molecule. Thus, in German Patent No. 741,462the production of new chromium compounds is described "Which are made upfrom one molecule of a metallisable dyestufi for example anunsulphonated o.o -dihydroxyazo dyestutf, one rnole cule of an aromatico-hydroxycarboxylic acid, for example salicylic acid or sulphosalicylicacid, and one chromium atom. They are obtained by displacing a moleculeof the aromatic o-hydroxycarboxylic acid in the complexsalicylatochromiates of the composition [Sa Cr(H O) 1M, (Sa=salicylicacid, M=alkali cation) by the metallisable o.o'-dihydroxyazo dyestutf onheating inaqueous solution or suspension. It has been found, however,that these complex compounds consisting of one molecule of themetallisable dyestuif, one chromium atom and one molecule of an aromatico-hydrox ycarboxylic acid easily make further changes underthe reactionconditions of the process sketched above. In"

particular, the action of the unmetallisedstarting dyestufii on thealready formed chromium complex of the type described above, bringsabout the formation offcomplex metal compounds which consist of twomolecules of dyestuft' and one chromium atom and which have differentproperties. For this reason, such unsymmetrical;

chromium containing dyestufis with a masked chromium atom are obtainedby the method described only in unsatisfactory yield and purity. In theproduction of such unsymmetrical, chromium containing dyestufis a2,824,094 Patented Feb. 18, 195s ice stuflfs' whichhiohtaina completemetal atom bound to feach"dyestuif molecule. However,;it is difficult,if not impossible, toobtain such metallised chromiumcomplexes ofunsulphonatedamonoazo dyestufiis of a ratio of 1 mol dyestuff to 1 molchromium in a pure form in art-aqueous medium... The process'in stepsinnon-aqueous solventsz is, a great technical disadvanta e.

It. .has: been found that comparatively stable, unsymmetrical complexheavy'metal compounds of metallisable azoz dyestufisiwhich-consist of Ta'dyestufi molecule, a metal.atomrandiaacomplex. former difierent fromthis dyestuff moleculegcan be obtained in aqueous or organic solution orsuspension by a reaction which produces practically;nobsideeproducts, ifsuch metallisable azo dyestuffs,whichwarexcapable of forming tricyclicchelates are ,treated in the-presence of co-ordinative divalent complexformersr withi agents giving off co-ordinative he avalentheavy metal 1 Amodification of theprocess consists in reacting .metal 0I Pl S.1QISisI-ing of one molecule .of an azo dyestuff capable of forming.tricyclic chelate and one atom of'a c oord in ative hexavalent heavymetal, .with co-ordinative divalen C mplex-formers.

u The characteristicof the process accordingcto thetpresentqinv tionithe 6, Of .aZO dyestutfs'gwhich are capable of forming tricyclicchelates whilst, in the processes already known azodyestufis areusedexclusively to form dicyelio chelates, for-example, o.o"-dihydrbxyazo,rocare boxy-offhydroxyazo or o-hydroxy d-amindazo diyestufis. Dyestuffsused according to the. present invention are capable of occupying, 4co-ordinationpositions at the complex forming heavy metal atom whilstforming. three 5 or 6 membercd ehelate rings whereas the dyestuffs usedup to the present occupy ,3 co-ordination,positions while forming only 2chelate rings. These tricyclic chelates; cause the, valences of .themetal formingthe complex to bets aturatedtto av greater degree andwhaveafar less tendency toform further complexes. than the dicyclic. chelates.They canbe ;very easily obtained therefore in aqueoussolutionor-suspension, also inthe presence of unmetallised startingdyestutf and in spite of this are capable of adding co-ordinativedivalentcomplex formers so that according to the choiceof .thecomponents, they can be given the desired dyeing properties. Thecapability: for the supplementary addition of co-ordinativedivalentcomplex formers is sufiicie'ntly great so that the desiredunsymmetrical metal complexes can be produced simply by metallising thedyestuffs inaqueous medium'in the presence of such, complex formers andthe masked metal complexes according to the present invention aresufficiently stable to. hinder the disadvantagesof too early fixationofthe, metal, on, the, wool. Thus, in contrast. to earlier, processes, it.isnneither' necessaryto use pre. viously prepared complex rnetallisingagents made up from excess. complex, formerand heavy metal salts for themetallising of the dyestufis, nor, in addition, is it; necessary ,topreparein a first stepunder special condi tions, the metalliseddyestutfhaving a ratio of 1 dyestuffj molecule, to 1 metal atom and toreact this ina second] step, witha colourless, complex former althoughit is also possible, and often very easy even, in, an aqueous medium,.toproduce first the so-called 1:1 complex and. then in the. same medium,to, addthe co-ordinativer divalent complex former. The new processaccording to.

wherein the free valences generally are bound to aromatic isoorheterocyclic rings A and B, one X represents an hydroxyl group, and theother X represents the radical in which D is a carboxymethyl, acarboxyethyl. an o-hydroxyphenyl, an o-carboxyphenyl or an 8-quinolinylradical, and n is one of the integers and l, the radical of aminoaceticacid -NHCH COOH, the radical of )8- aminopropionic acid NHCH -CH COOH,the 0- carboxyphenylamino radical, the o-hydroxyphenylamino radical, thequinolinyl-(8)-amine radical, the sulphonic acid glycinide radical, thesulphonic acid amide-B-propionic acid radical, the sulphonicacid-o-carboxyphenylamide radical, the sulphonicacid-o-hydroxyphenylamide radical, etc. The radical X can be either inthe diazo or also in the coupling component. Diazo components for .theproduction of the dyestuffs usable according to the present inventionare, for example, Z-aminobenzene-l-sulphonic acid amides which containan acetic acid, propionic acid, o-hydroxyor o-carboxy-phenyl radical assubstituents at the nitrogen atom of the amide group and wherein thearomatic rings can be further substituted as desired. The diazocompounds thereof are coupled, for example, with acylacetic acidarylamides, S-pyrazolones, phenols and naphthols coupling in theo-position to the hydroxyl group, to form the azo dyestutfs usableaccording to the present invention. Azo dyestuffs usable according tothe present invention are also obtained by coupling diazotised2-amino-l-hydroxy compounds and Z-amino-l-carboxylic acids of thearomatic series with azo components coupling in the neighbouringposition to the substituted amino group, the substituent of the aminogroup being, for example, the acetic acid radical, the propionic acidradical, an o-carboxy, or o-hydroxyphenyl radical. Examples of suchcoupling components are Z-naphthyl-fi-amino-propionic acid,Z-(o-carboxyphenylamino)-naphthalene, 2-(0-hydroxyphenylamino)-naphthalene, in which compounds too the aromaticrings can be further substituted. Suitable azo dyes therefor correspondto the formula:

wherein A represents a radical of the benzene series containing thehydroxyl group in o-position to the azo group, B represents a radical ofthe naphthalene series bound to the azo group in l-position andcontaining the pounds, o-amino-hydroxyaryl compounds, 8-hydroxy+quinolines or benzoquinolines, aromatic o-hydroxyaldehydes, aromatic ohydroxy ketones, o-hydroxyazo and o? hydroxybenzene azo methinecompounds, 1.2-diaminoalkanes, pyridine and benzopyridine-Z-carboxylicacids and o-nitrosonaphthols. These can be more closely adapted to thedesired purpose by further substitution, preferably in aromatic rings,by halogen, sulphonic acid, sulphonic acid amide groups.

By the suitable choice of a co-ordinative divalent complex former, it ispossible to favourably improve, for example, the drawing power on towool, the levelling power and the non-selective dyeing of difierentqualities of wool of a certain tricyclic metallised azo dyestutf.

In the process according to the present invention, chiefly chromium andpossibly also cobalt can be used as complex forming co-ordinativehexavalent heavy metal. The usual salts of these metals can be used asmetal-yielding agents; often in the chroming of unsulphonated azodyestufis in aqueous solution or suspension, the complexchromocsalicylates can be used with advantage. The new process isparticularly valuable in the production of unsulphonated tricyclicmetallised dyestuffs. By this process often particularly pure complexchromium compounds which draw well on to wool from a neutral to weaklyacid bath can be produced.

The following examples illustrate the invention without limiting it inany way. Where not otherwise stated, the parts are given as parts byWeight and the temperatures are in degrees centigrade. The relationshipof parts by weight to parts by volume is as that of kilogrammes tolitres.

Example 1 29.2 parts of Z-aminobenzene-l-sulphonicacid-(2'-carboxyphenylamide) are dissolved with 8 parts of sodiumhydroxide in parts of hot water and 6.9 parts of sodium nitrite areadded. The cooled solution is slowly added dropwise at 0-5 to a mixtureof 46 parts of concentrated hydrochloric acid and 100 parts of water.The reaction mixture is then neutralised with sodium bicarbonate andpoured at 0-3 into a solution of 22 parts of1-(3-chlorophenyl)-3-methyl-5-pyrazolone and 4 parts of sodium hydroxidein 400 parts of water. On completion of the dyestulf formation, thedyestufl? is precipitated by the addition of sodium chloride, filteredoff and dried. The dyestufl is then heated in 250 parts of formarnidewith chromic acetate (corresponding to 5.2 parts of chromium) and 15parts of 8-hydroxyquinoline for 2 /2 hours at and the yellow solutionformed is poured into a mixture of parts of concentrated hydrochloricacid and 2000 parts of water. The chromium containing dyestuffprecipitates. It is filtered off, washed with water, stirred in 250parts by volume of 0.5 N-caustic soda lye for 15 minutes at 80-90,precipitated by the addition of sodium chloride, filtered off and dried.It is a yellow brown powder and it dyes wool from an acetic acid bath ingreenish-yellow shades. The dyeiugs are very level and are distinguishedby good fastness properties.

Example 2 23.2 parts of 5 nitro 2 amino 1 hydroxybenzene- 4-methylsulphone are pasted in 150 parts of glacial acetic acid and 18 parts ofconcentrated hydrochloric acid and 6.9 parts of sodium nitrite asconcentrated aqueous solution are added at 20-25. 27.6 parts of 2-(2-carboxyphenyl)-naphthylarnine are added and the whole is heated to50-60. On completion of the dyestutf formation, the dyestuif whichprecipitates in crystalline form is filtered off, washed with aceticacid and then with hot water and dried. It is then dissolved in 200parts of formamide with 13.3 parts of 30% caustic soda lye, and heatedfor 1% hours at 125-l30 with chromic acetate (corresponding to 5.2 partsof chromium) and 16 parts of S-hydroxyquinoline. The reaction mixture ispoured into- 2000 parts of an 80 warm 15% sodium chloride solution,neutralised with caustic soda lye and the dyestufi which hasprecipitated is filtered off. It is a complex chromium compoundcontaining one atom of chromea ow dried.

6 action mixture-is poured on to 2000 parts of 15% sodium chloridesolution, thedyestuiiis filtered ojtf and It is a green powderwhichmdyes.woolfroma t weakly acid bath in pure green shades which havevery OH good fastness properties.

Example 5 18.9 parts of 5 nitro 4 chloro 2 amino l hy-' a droxybenzeneare diazotised as described in Example 2 and coupled with 27.6 parts of2-(2'-earboxyphenyl)- SO2OHB naphthylamine. The dried dyestufi in 450parts of ethand with one molecule of 8-hydroxyquinoline, and is a yleegly p monomethyl ether boiled-Hilde? reflux green p wd hi h d l f e klyid b h withchrorriic acetate (corresponding to 5.2 parts of chroi pureyellowish green h d Th td i h vgry mium in 300 parts of water) until thestarting dyestutf d f m g roprties has disappeared. 52 parts of sodiumacetate and 14.8 parts 'of'picoli'nic acid are addedandthewholeis againE my 3 boiled fo r-2 hoursunder reflux. The reaction mixture The metalfreedyestuff obtained according to Example 15 diluted with F FE il? prcigi alq y i is m- 2 is dissol ved in750 parts of water with 4 parts ofsoteredofi- After F .1! lsuafirfien powderwhlch dyes dium hydroxide.Cobalt acetateteorresponding: to 5 ,9 W99 #9! n mm @9 5 h" f 1 8 1 1. ssparts of cobalt) is added at 70", sodium carbonate is i added until thereaction is phenolphthalein alkaline and Example 6 the whole'is stirredat 7080" until all the starting dye- 32.8 parts of 3 amino 4 hydroxy 3sulphamidostuff has disappeared. 17.4 parts of '8-hydroxyquinolinedipheriyl'sulphone are diazotisediaccording to Example are added and thewhole is stirred for 2 hours at 70-80". 2 and coupled with 27.6 parts of2-(2-carboxyphenyl)- The 'dyestufi which has completely precipitated, isfilnaphthylamine. The dried dyestufr" is heatedfor 1 h our tered off anddried. It is a complex cobalt compound at l20-l30 in 250 parts ofacetamidewith chromic ace,- containing one atom of cobalt in complexunion with one tate (corresponding to 5.2 parts of chromium). Themolecule of the dyestufi of the formula mixture is poured on to. 1000parts of 15 %.sodium chlo- 000E, ride solution the dyestufi-isfilteredofi and pasted in 750 parts of water. Sodium carbonate is added untilthe 0H NH reaction is phenolphthaleiu alltaline, 19.8 parts oi 5-chino-81hydroxyquinoline;area added and the whole is, heated for l hour;at 30-20? The dyestuti; is complete. ly precipitated by the addition ofsodium chloride and filtered oil. It is a green powder which dyes woolfrom a neutral to weakly acid bath in pure green shades which have verygood fastness properties. and with one molecule of 8-hydroxyquinoline,and is a Example. 7: dark green powder which q Wool from a weakly acld18.7 parts of 2-amino-l-hydroxybenzene-A-methyl sulbath i green Shadeswhich have very 599d 'fi phone are diazotised as described in Example 2and coupmpertles' pled with 27.6 parts of2-(2'-carboxyphenyl)-naphthylttf 4 amine. The dyestuff, after beingwellwashed, is dis- The metal free dyestufi obtained according toExamsolved in 600'parts of water with 8parts'of sodium hy ple. 2isdissolved in 200 'parts of formamide with 13.3 droxide and is boiledunder reflux with 225 parts of a parts of 30% caustic soda lye andheated.with chromic solution of ammonium chromosalicylate(correspondingacetate (corresponding to' 5.2 parts of chromium) for to5.2 parts of chromium)untilthe metallisation is com- 1% hours at120-,-125".. The mixture. is poured into plete. The dyestuff isprecipitated by the addition of so- 1000 parts of saturated sodiumchloride solution, the dium chlorideand filtered off. It is a greenpowder precipitated dyestutf is filtered 01f and dried. It is then whichdyes wool from an. acid bath in; fast bluish-green stirredin SOOparts ofalcohol. 28 parts of sodium acew shades. This chromium containingdyestuff contains corate and a solution ofi 12.3 parts ofsalicylaldehyde and ordinated salicylic acid. Y 9.3 partsof aniline-in100 parts of alcohol areaadded; and The following dyestuflfs areobtained in the manner the whole is boiled under refluxfor 3 hours. The116- described in the above examples:

No. Dlazo component A20. component Complex formerv Metal Qolour on wool1....-. s-nitrozamino-1-hydroxybenzene2-(2'-carboxypheny1)-naphthylanilne.- 8 -hydro xyquinol lne..'.. CrYellowish 2 snitrol-chloro-Z-amino-l-hydroxybenzene. n Co c5533? 34-nitro-2-amino-1-hydroxybenzenedo Or Yellowish 4 Z-amino 1-hydroxybenzene-4-ethyl an n Cr iI sulphone. 5 5-nltro-2amlnobenzoie rido do Or Blulsh green. 6 5-nitro-2-amino-bhydroxyhenzenei- Or Yellowishethyl sulphone. green. 7 5-nitro-2-amino-1-hydroxybenzene-4- 2 (5'chloro 2 carboxyphcnyl) .....do Cr Do.

methyl sulphone. naphthylamine. 8 .do 2-(fl-carboxyethyD-naphthylamlned0 Bluish green.

2-(2-carboxyphe nyl)-naphthylnmlne' Sallcylaldehyde :Green.o-klydroxyacetophenon Do.

11-.... 5-nttro-4-chloro-2-amlno-1-hydroxydo CH=N-CH1 Cr Yellowishbenzene. green.

No. Dlazo component 7 A20 component Complex former Metal Colour on wool12... 5 nltro 2 a'mlno 1 hydroxybenzene do GH=N r Green.

4-methylsulphone.

13..." do 2 (5' chloro 2' carboxyphenyl) 0H=NG|H, Or Do.

naphthylamlne.

14 do 2(2'-carboxyphenyl)-naphthy1amine-- Qulnaldic acid Or Yellowishgreen. 15 -do d0 5 hydroxy azo (4) phen- Or Do.

anthrenc. 16".-. 4.G-dinitro-Zamino-l-hydroxybenzene d0 Salicylic acidCr Green. 17.- 2- aminobenzene 1 sulphonlc aeld- (2' 2-naphthol n CrRed-brown.

carboxyphenylamide). 18 3 amino 4 hydroxy 3 sulphamido2-(2-carboxyphenyl)-naphthylamlne.- S-hydroxyqulnoline Cr Green.

diphenyl sulphone. 19 5 nitro 2 amino 1 hydroxybenzene ..do Picolinicacid Or Do.

4-methyl sulphone. 20 Z-amlnobenzoic acid "do S-hydroxyquinoline CrBluish green. 2l- B-nltro-2-amino-l-hydroxybenzcne2-(Bcarboxyethyl)-naphthylam .do Cr Green. 22--.Z-aminobenzene-l-sulphonic acid glycluide1-phenyl-3m1ethyl-5-pyrazol0ne.- Cr Gresfillsh ye ow.. 23 d07-methoxy-2'naphtho1 .do Or Red-brown. 24-.. 2 amlnobenzene 1 sulphonicacid (2 2-naphth0l S-hydroxyquinoline Or Do.

hydroxyphenylamide). 25 do 1-pheny1-3-methyl-5-pyrazolone Salicylic acidCr Reddishyellow.

Referring to representative ones of the products of containing one atomof chromium in complex union with the preceding table: one molecule ofthe dyestufi of the formula Product No. 4 is a complex chromium compoundcon- COOH taining one atom of chromium in complex union with onemolecule of the dyestutf of 'the formula V 0H H 0 O OH l N=N ON =N 4oand with one molecule of picolinic acid.

SOPCH What we claim is: 1. A chr mifer u o h' c n ai 0 atom and with onemolecule of 8-hydroxyqumol1ne; 4 o o s c mpound w lch o t us ne ofchromium in complex union with one molecule of an unsulphonated monoazodyestufi capable of forming tricyclic chelates and which corresponds tothe formula:

Product No. 6 is a complex chromium compound containing one atom incomplex union with one molecule of the dyestuff of the formula wherein Arepresents a radical of the benzene series containing the hydroxyl groupin o-position to the azo group, B represents a radical of thenaphthalene series bound to the azo group in l-position and containingthe 80202155 NH D COOH and with one molecule f g h d i li V radical in 2position, D represents an o-phenylene radical, product No. 13 is acomplex chromium compound and with one molecule of a coordinativedivalent complex containing one atom f hf i in complex union with formercontaining a metallizable structure selected from one m l ul of h d t fff the fo la the group consisting of structures of the formulae:

. l r e '1 K V SONH and with one molecule of 8-hydroxyquinoline; and f\O/ Product No. 19 is a complex chromium compound ll and 5. The complexchromium compound which contains H one atom of chromium bound in complexunion to one molecule of the dyestufi? of the formula: 2 (l 5 COOH v IOH IIIH and of the tautomeric forms thereof.

2. A chromiferous compound which contains one atom of chromium incomplex union with one molecule of an 1 O N unsulphonated monoazodyestufl capable of forming tri- 2 cyclic chelates and which correspondsto the formula: 5102mm OH NHDCOOH A and to one molecule ofS-hydroxyqumohne.

6. The complex chromium compound which contains one atom of chromiumbound in complex union to one molecule of the dyestufi of the formula:

wherein A represents a radical of the benzene series containing thehydroxyl group in o-position to the azo group, B represents a radical ofthe naphthalene series bound to the azo group in l-position andcontaining the 0 00011 -NHD--COOH o 0 o e radical in 2-position, Drepresents an o-phenylene radlcal, and with one molecule of8-hydroxyquinoline.

3. The complex chromium compound which contains one atom of chromiumbound in complex union to one molecule of the dyestuif of the formula:

coon t-Q OH SOzNH r and to one molecule of S-hydroxyquinoline.

7. The complex chromium compound which contains 0 N one atom of chromiumbound in complex union to one molecule of the dyestufl of the formula:

802011;: (FOOT! and to one molecule of S-hydroxyquinoline. H \TE 4. Thecomplex chromium compound which contains one atom of chromium bound incomplex union to one molecule of the dyestuff of the formula: T M

coon

=N and to one molecule of picolinic acid.

References Cited in the file of this patent UNITED STATES PATENTSsot-W15 1,994,116 Straub et a1. Mar. 12, 1935 and to one molecule of8-hydroxyquinoline. 2,551,056 Schetty May 1, 1951

1. A CHROMIFEROUS COMPOUND WHICH CONTAINS ONE ATOM OF CHROMIUM INCOMPLEX UNION WITH ONE MOLECULE OF AN UNSULPHONATED MONOAZO DYESTUFFCAPABLE OF FORMING TRICYCLIC CHELATES AND WHICH CORRESPOND TO THEFORMULA: